Liquid detergent composition containing solubilizing electrolytes



Oct. 10, 1

Temperature 967 K w. HERRMANN LIQUID DETER'GENT COMPOSITION CONTAINING SOLUBILIZING ELECTROLYTES Filed April 21, 1966 Melting Point I Surfactant in Water Kenneth W. Herrmonn I INVENTOR.

A'r-roaneY LIQUID; DETERGENT COMPOSITION CONTAIN- IN G SOLUBILIZING' ELECTROLYTES Kenneth W. Herrmann, Greenhills, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio Filed Apr. 21, 1966, Ser. No. 549,754

6 Claims. (Cl. 252- 137) This applicationis a continuation-in-part of copending application Ser. No. 421,142, filed Dec. 14, 1964, now

certain solubilizing electrolytes.

The formulation of liquid detergent compositions is very complex. Ordinarily, it is desirable to keep inert .ingredients at a minimum and yet it often becomes necessary to add some compound to the formula which has no active detergent effect or detergency builder effect merely to make the active ingredients compatible with each other and thereby create a homogeneous composition (i.e., a composition in which there is no bulk separation of a phase). It would therefore be desirable to provide, in liquid detergent compositions, effective, low cost solubilizing agents to replace all or part of the usual organic solubilizing agents and solvents.

Accordingly, it is an object of this invention to provide homogeneous liquid detergent compositions.

It is a further and more specific object of this invention to provide such compositions containing solubilizing electrolytes and certain specific detergents.

The aqueous homogeneous liquid detergent compositions of this invention which achieve these objects comprise:

(I) From about 1% to about 40% by weight of the composition of a detergent selected from the group consisting of (A) A detergent having the formula (sultaine detergent) wherein R and R are each selected from the group consisting of hydrogen, methyl, and ethyl groups, R is a straight chain alkylene group containing from two to four carbon atoms, and having from to one hydroxyl group substituted on a secondary carbon, and R is an alkyl chain of from about to about 20 carbon atoms;

(B) A detergent having the formula R' R R P O (phosphine oxide detergent) wherein R isselected from the groups consisting of alkyl, and alkyl monohydroxy radicals containing from about 8 to about 16 carbon atoms and R and R are each selected from the group consisting of alkyl radicals and alkanol radicals containing from one to about three carbon atoms; and

' (C) Mixtures thereof;

(II) From 0% to about 40% by weight of the composition of a polyvalent electrolyte salt selected from the group consisting of sulfates; carbonates; pyrophosphates; phosphates; hexametaphosphates; ethylenediaminetetraacetates; N (2-hydroxyethyl)-ethylenediaminetriacetates; nitrilotriacetates; N (2 hydroxyethyl)-nitrilodiacetates; phytate's; ethane-l-hydroxy-1,1-diphosphonates; methylene diphosphonates; ethylidene, isopropylidene, benzylmethylidene and chloromethylidene diphosphonates; salts of polymers of itac-onic acid, aconitic acid, maleic acid, mesa- United States Patent 0 ice conic acid, fumaric acid, methylene malonic acid and citraconic acid and copolymers with themselves and ethylene; and mixtures thereof, the cations of the above polyvalent electrolytes being selected from the group consisting of sodium, potassium, ammonium, triethanol ammonium, diethanol ammonium and monoethanol ammonium cations and mixtures thereof;

(III) From about 0.5% to about 20% by weight of the composition and sufiicient to keep the composition homo geneous, of inorganic solubilizing electrolytes having a monovalent anion with a volume greater than 25 A., said volume being calculated using P-aulings ionic radius for monoatomic anions and a radius equal to the sum of the largest interatomic bond distance and. the radius of the outer atom for polyatomic anions; and

FIGURE 1 is a representative phase diagram for the V sultaine detergents utilized in the compositions of this invention as hereinafter more fully discussed.

The first group (A) of the specific detergents, as hereinbefore described, will be referred to hereinafter as sultaines or sultaine detergents. These sultaines are solubilized, according to the instant invention, in an aqueous solution by the solubilizing inorganic electrolytes hereinbefore named. Sultaines of particular interest are those in which the long alkyl chain (R) is a mixture of alkyl chains derived from naturally occurring substances, whether hydrogenated or not, and the short alkyl chains are methyl groups. For instance,.where R is derived from tallow or coconut oil, R contains three carbon atoms with a hydroxyl group substituted on the middle carbon atom, and R and R -are methyl groups, the sultaines are of particular interest since they are readily prepared.

Specific examples of the above sultaines include 3-(N,N- dimethyl-N-hexadecyl ammonio)-propane-1-sulfonate, 3- (N-hexadecylammonio) -propane-'1sulfonate, and 3 N,N- dimethyl-N-hexadecyl ammonio)-2-hydroxypropane-1-sulfonate. Other specific examples include the corresponding decyl, dodecyl, tetradecyl, and octadecyl homologs of the above compounds.

Of special interest as regards the solubilizing electrolytes of this invention are relatively water-insoluble sultaines wherein R is an alkyl chain of '(1) from about 12 to about 18 carbon atoms. when R and R are hydrogens, (2) from about 16 to about 20 carbon atoms when R R and R contain no substituents, and (3) from about .14 to about 18 carbon atoms when R and R are alkyl chams, and R is a three carbon atom alkylene group with a hydroxyl group substituted on the middle carbon atom. The solubilizing electrolytes of this invention solubilize the crystalline phase of these sultaines as hereinafter described.

Specific examples of the posphine oxide detergents include:

dimethyldodecylphosphine oxide dimethyltetradecylphosphine oxide ethylmethyltetradecylphosphine oxide cetyldimethylphosphine oxide dimethylstearylphosphine oxide cetylethylpropylphosphine oxide diethyldodecylphosphine oxide diethyltetradecylphosphine oxide dipropyldodecylphosphine oxide bishydroxymethyl dodecylphosphine oxide bis (Z-hydroxyethyl) dodecylphosphine oxide (Z-hydroxypropyl)methyltetradecylphosphine oxide dimethyloleylphosphine oxide, and diniethyl-(Z-hydroxydodecyl)phosphine oxide and the corresponding decyl, hexadecyl, and octadecyl homologs of the above compounds. These phosphine oxide detergents are solubilized, according to the instant invention, in an aqueous solution by the solubilizing inorganic electrolytes hereinbefore named.

All the detergents of this invention normally contain mixtures of long alkyl chains (R and R). These can be derived from naturally occurring substances such as tallow and coconut oil, and can also be derived from petroleum fractions, e.g., by polymerizing propylene or cracking waxes to form the proper chain length, e.g., in the form of olefin. The method of deriving the alkyl chain is immaterial. The alkyl chains can be unsaturated.

The liquid detergent compositions of this invention contain from about 1% to about 40% by weight of the composition of the detergents hereinbefore described. The minimum amount is set by practical product considerations of detergency benefits derived per unit volume. The upper limit, on the other hand, is set by several considerations including viscosity, crystalline solubility, and the possibility of forming liquid mesomorphic phases or an insolubilizable, immiscible second isotropic phase.

Although it is not desired to be bound by theory, it is believed that certain inorganic electrolytes having an anion with relatively low charge density (ratio of number of charges in the anion to volume of the anion) are most ettective in preventing phase separation in the compositions of this invention. The effective anions are singly charged. Therefore, the anions with large volumes are effective. For these solubilizing inorganic anions the volume of the anion should be at least about 25 A. This volume is calculated using Paulings ionic radius for mon-oatomic atoms and a radius equal to the sum of the longest interatomic bond distance plus the radius of the outer atom for polyatomic anions. These interatomic distances and atomic radii can be obtained by consulting The Nature of the Chemical Bond, Linus Pauling, Cornell University Press (1939).

The following are illustrative of the calculations. The radius of the iodide anion is 2.16 A. (op cit., p. 346). This corresponds to a volume of 4/3 1r (2.16) or approximately 42 A. The volume of a nitrate anion is determined by first adding the radii of the nitrogen and the oxygen to determine the interatomic [0.70 A. (radius of nitrogen)-|-O.66 A. (radius of oxygen)=1.36 A.] distance between nitrogen and oxygen. Then the radius of the oxygen (0.66 A.) is added to the interatomic distance. (1.36 A.+.66 A.=2.02 A.) The volume of the nitrate anion is then 4/3 11' (2.02) or approximately 35 A. These inorganic solubilizing electrolytes include the alkali metal, ammonium, and substituted ammonium chlorides, bromides, and iodides such as sodium chloride, potassium chloride, sodium bromide, potassium bromide, ammonium chloride and tn'ethanolammom'um chloride and the corresponding iodides; and alkali metal, ammonium and substituted ammonium chlorates, nitrites, bromates, iodates, perchlorates, thiocyanates, periodates, bicarbonates, borates, and nitrates such as sodium, ammonium and potassium chlorates, and sodium, ammonium, monoethanolammonium, diethanolammonium, and potassium nitrates.

Variation in degree of effectiveness is found in solubilizing the various detergents with the various solubilizing electrolytes. Inorganic solubilizing electrolytes with smaller inorganic anions such as the chloride anion have a generally much lower degree of effectiveness, however, sodium chloride is desirable for solubilizing the rela- 4t tively insoluble sultaine surfactants as hereinafter described since it is inexpensive.

The solubilizing electrolytes of this invention are used in an amount from about 0.5% to about by weight of the liquid detergent composition and sufficient to provide a homogeneous composition. Preferably only sufficient solubilizing electrolyte is used to create a single phase in the temperature range desired. This temperature range is usually from about 40 F. to about 120 F.

It will be understood that where the sole separating phase is one which is not affected by the action of the solubilizing electrolyte, e.g., where the sole separating phase is crystalline inorganic builder, there is no benefit from using a solubilizing electrolyte. These solubilizing electrolyes can be used in combination with other solubilizing agents and solvents which solubilize other separating phases.

With respect to the separating phases solubilized by the inorganic solubilizing electrolytes hereinbefore described, the presence of a second immiscible isotropic liquid phase can be a function of temperature. As the temperature of the composition is raised, a second liquid phase separates. For some detergents this separation occurs only when a polyvalent electrolyte, e.g., builder, is present. The solubilizing electrolytes of this invention raise the temperature at which this separation occurs, whereas other electrolytes having anions with relatively high charge densities have generally the opposite effect, i.e., promote separation at lower temperatures. Examples of electrolytes which tend to cause a separation of a second isotropic liquid phase include many of the common ingredients found in detergent compositions such as the polyvalent electrolytes hereinbefore mentioned, e.g., potassium and sodium pyrophosphates, sodium and potassium tripolyphosphates, potassium and sodium silicates, potassium and sodium sulfates, potassium and sodium ethylenediamine tetraacetates, and sodium and potassium nitrilo triacetates.

The presence of a temperature-dependent second liquid phase which exists without a polyvalent elec trolyte being present is a function of detergent molecular structure and cannot readily be predicted. In general, with respect to the hydrophobic group, the longer chain lengths are less soluble and more prone to exhibit this phenomenon. With respect to the hydrophilic group, phosphine oxide detergents are more likely to exhibit this phenomenon, whereas anionic detergents generally do not. A primary benefit from the use of solubilizing electrolytes in a liquid composition of this invention is derived whenever a second liquid phase, as hereinbefore described, is the separating phase.

When used with the relatively water-insoluble sultaine detergents hereinbefore described, the electrolyte solubilizing agents of this invention are present in the liquid detergent composition in an amount from about 0.5% to about 20% by weight of the liquid detergent composition and sufficient to lower the Krafft temperature of the sultaine detergent in the liquid detergent composition below about 70 F. (room temperature), preferably below 40 F., to prevent the crystalline detergent from separating out of solution during normal use and storage.

These particularly relatively water-insoluble sultaine detergents are unique in that the addition of the electrolytes of this invention to their aqueous solution lowers their Kraift temperature as hereinafter more fully described. This Krafft temperature is really a narrow range 'of temperature for a given compound within which a small increase in temperature gives a very large increase in solubility of the crystalline surfactant. Lowering of the Krafft temperature for a given sultaine-electrolytewater system has the practical effect of raising the solubility of the surfactant in water for any temperature which is above the temperature to which the Kraift temperature is lowered and which is below the Kraift temperature of the surfactant in water (without solubilizing electrolyte). Normally, the addition of an electrolyte to an aqueous anionic surfactant solution will raise this Krafft temperature (lowering practical solubility), but the addition of the electrolytes of this invention to the sultaine detergents utilized in the compositions of this invention lowers their Krafft temperature (increases practical solubility).

The effect of this lowering of the Kraflt temperature is such that homogeneous liquid detergent formulations can be prepared containinga considerable amount of sultaine detergent by theuse of solubilizing electrolytes. To explain, the mechanism by which these particular electrolytes solubilize these sultaine detergents, reference is .made to a phase diagram typical of the liquid systems of this invention, FIG. 1, in which the crystalline solubility (to left of point A) of a representative sultaine detergent of this invention in water is plotted as a function of temperature with a solid line (Tw is the Kraift temperature of the sultaine detergent in water) and the crystalline solubliity (to the left of point A of the same representative sultaine detergent in an aqueous solubilizing-electrolyte solution of constant concentration is plottedas a function of temperature with a broken line (T is the Kratft temperature of the sultaine detergent in electrolyte solution). It Will be understood that the position of this broken line varies with the concentration of solubilizing-electrolyte in water and that there is a series of these broken line curves for different electrolyte concentratitons. Up to a certain limit, the more electrolyte that is present the lower the broken line curve is on the diagram.

The lines on the diagram represent the boundaries for homogeneous solutions. Region B is homogeneous and is commonly referred to as nigre; regions C and C are characterized by the presence of liquid mesomorphic phase; regions D and D are characterized by the presence of another liquid mesomorphic phase; and region E is characterized by the presence of crystals of detergent plus detergent solution. When the addition of the solubilizing-electrolytes of this invention lowers the Krafft temperature of the sultaine detergent, as hereinbefore described, below the temperature of the liquid detergent composition, the crystalline solubility of the sultaine detergent in water is substantially increased. The practical result is that a greater amount of the sultaine detergent can be used in the detergent composition while maintaining homogeneity. In general, the liquid compositions of this invention containing the relatively water-insoluble sultaines will be to the left of A and A on the accompanying sultainewater phase diagram (FIG. 1). (A and A are the crystalline solubility points hereinbefore described.) The amount of lowering of the Kraift temperature is dependent upon the amount and, particularly, the type of electrolyte present as well as the molecular structure of the sultaine.

In addition to the detergents and solubilizing agents hereinbefore described, the detergent compositions can also contain from 0% to about 40% by weight of the composition of polyvalent electrolytes, but no more than can be dissolved in the compositions. These polyvalent electrolytes can be inert salts, which are associated with the detergent materials, such as sodium sulfate or can be desirable detergent builder electrolytes. Examples of water soluble inorganic alkaline detergency builder salts are alkali metal carbonates, phosphates, polyphosphates, and silicates. Specific examples of such salts are sodium and potassium tripolyphosphates, carbonates, pyrophosphates, phosphates, and hexa'metaphosphates. Examples of organic alkaline sequestrant builder salts are (l) alkali metal amino polycarboxylates [e.g., sodium and potassium ethylene diaminetetraacetates, N-(2-hydroxyethyl)- ethylene diamine triacetates, nitrilo triacetates, and N- (Z-hydroxyethyD-nitrilo diacetates]; (2) alkali metal salts of phytic acid (e.g., sodium and potassium phy- 3,213,030); (5) water soluble salts of substituted vmethylene diphosphonic acids (e.g., trisodium and tripotassium ethylidene, isopropylidene, benzylmethylidene, and

halomethylidene diphosphonate's and 'the other substituted methylene diphosphonates disclosed in the copending application of Clarence H. Roy, Ser. No. 266,055,

filed Mar. 18, 1963);"(6) water soluble salts of polycarboxylic polymers and copolymers as'described in the copending application'of Francis L. Diehl, Ser. No'. 269, 359, filed Apr. 1, 1963, now Patent No. 3,308,067, i.e., a polyelectrolyte builder material consisting of watersoluble salts of a polymeric aliphatic polycarboxylic acid selected from the group consisting of i (a) water-soluble salt of a homopolymer of an aliphatic polycarboxylic acid having the following empirical formula:

X Z I I Y C O OH 11 wherein X, Y, and Z are each selected from the group consisting of hydrogen, methyl, carboxyl, and carboxymethyl,

at least one of X, Y, and Z being selected from the group consisting of carboxyl and carboxymethyl, provided that X and Y can be carboxymethyl only when Z is selected from carboXyl and carboxymethyl, wherein only one of X, Y, and Z can be methyl, and wherein n is a whole integer having a value within a range, the lower limit of which is three and the upper limit of which is determined by the solubility characteristics in an aqueous system;

(b) a water-soluble salt of a copolymer of at least two of the monomeric species having the empirical formula described in (a) and,

(c) a water-soluble salt of a copolymer of a member selected from the group of alkylenes and monocarboxylic acids with the aliphatic polycarboxylic compounds described in (a), said copolymers having the general formula:

1' R X Z H I i (l-m) 1 30 OH in wherein R is selected from the group consisting of hydrogen,

methyl,

carboxyl, carboxymethyl, and carboxyethyl;

wherein only one R can be methyl; wherein m is at least 45 mole percent of the copolymer; wherein X, Y, and Z are each selected from the group consisting of only one of X, Y, and Z can be methyl and wherein n is a whole integer within a range, the lower limit of which is three and the upper limit of which is determined primarily by the solubility characteristics in an aqueous system; said polyelectrolyte builder material having a minimum molecular weight of 350 calculated as the acid form and an equivalent weight of about 50 to about 80, calculated as the acid form, (e.g., polymers of itaconic acid, aconitic acid; maleic acid; mesaconic acid; fumaric acid; methylene malonic acid; and citraconic acid and copolymers with themselves and other compatible monomers such as ethylene); and (7) mixtures thereof.

Mixtures of any and all of the organic and/or inorganic builders can be used and are generally desirable. Especially preferred are the mixtures of builders disclosed in the copending application of Burton H. Gedge, Ser. No. 398,705, filed Sept. 23, 1964, e.g., ternary mixtures of sodium tripolyphosphate, sodium nitrilotriacetate, and sodium ethane-l-hydroxy-1,1, diphosphonate.

Other ingredients can also be present in the liquid detergent compositions of this invention without detracting from the advantageous properties of the invention.

Anti-redeposition agents such as carboxymethylcellulose and anionic, cationic or nonionic detergents can also be added. Typical minor additives which can be present include suds boosters and suppressants, dyes, opacifiers, perfume, corrosion inhibitors and anti-microbial agents.

All percentages, ratios and parts herein are by weight unless otherwise specified.

The practice of this invention is demonstrated in the following examples.

Example I Aqueous mixtures were prepared with 1% by weight of the mixture of a sultaine detergent with the formula and 1% of the following electrolytes. Since 1% of this sultaine detergent is not normally soluble in water, observations were made as to the temperature at which the mixture clouded on cooling and cleared upon heating after 15 minute equilibration. The temperature was changed in increments. These observations are indicative of crystalline detergent solubility and solubilization. The different results obtained on heating and cooling are explainable due to the non-equilibrium conditions employed. Where there are large differences, supersaturation on cooling undoubtedly occurred.

The first three electrolytes are examples of the solu bilizers of the invention and the rest show the relative ineffectiveness of conventional electrolytes in increasing the solubility of crystalline sultaine.

Similar aqueous mixtures of 1% by weight of the mixture, of the same sultaine detergent were prepared with varying concentrations of the same electrolytes Cir (same anions) to determine how much electrolyte was necessary to clear the mixture at room temperature (approximately 27 C.). Percent by Weight of inorganic solubilizing electrolyte Inorganic solubilizing electrolyte:

NaI 0.8 NaCl 1.0 NaClO 0.5 NaSO Saturated solutions of Na SO these electro- K P O lytes failed to solubi- Tetrasodium ethylene dilize the 1% sultaine amine tetraacetate detergent.

More aqueous mixtures were prepared with the same sultaine detergent to determine how much of the crystalline surfactant was soluble at room temperature when 1% of some preferred electrolyte solubilizing agents was Present Sultaine detergent Electrolyte: gms./ gms. of Water NaClOfi NaI NaCl 2.8 NOI1, Na PO4, NB2SO4, and K4P207 0.

Mixtures of 5% by weight of the mixture of a sultaine surfactant with the formula CH3 1aHas-l I CaHa-S 0 3 and 1% by weight of the mixture of various inorganic electrolytes were prepared and observations were made of the temperature at which the crystalline surfactant became soluble on heating and cooling as evidenced by the cloudiness or clarity of the mixture.

Electrolyte Clouds on Clears on Cooling C.) Heating C.)

0 to 4 0 to 4 The mixtures containing water, the above sultaine detergent and the NaI, NaNO and NaClO solubilizing inorganic electrolytes were homogeneous detergent compositions which maintained their homogeneity over a broad temperature range.

Example III Mixtures containing 1% by weight of the sultaine detergent of Example I, 10% K4P2O7, and 1% by weight of various electrolyte solubilizing agents of this invention were prepared and the temperature at which the mixture became homogeneous was determined by observing the point at which the mixture became cloudy or clear upon heating and cooling.

Electrolyte Clouds on Clears on Cooling C.) Heating C.)

9 When in the above example, any of the following detergent compounds, or mixtures of the following compounds, are substituted for the specific sultaine deterthe corresponding compounds wherein N-met'hyl groups are substituted for N-hydrogens and/ or N-ethyl groups; N-ethyl groups are substituted for N-hydrogens and/or N-methyl groups; N-hydrogens are substituted for N- methyl and/or N-ethyl groups; the corresponding compounds wherein decyl, dodecyl, tetradecyl, hexadecyl, 'octadecyl, eicosyl, oleyl, linoleyl, linolenyl, 4-propyldodecyl, tetrapropyl, tetrabutyl, pentadecyl, and heptadecyl groups are substituted for the long alkyl chains in the above compounds.

Example Illa Aqueous mixtures containing 1% by Weight of dimethyldodecyl phosphine oxide and the indicated percentagesby Weight of the indicated inorganic solubilizing electrolytes (these percentages are equivalent on a molar basis-0.2 molar) and builder electrolyte were prepared and the lowest temperatures above which the mixtures were two phase were determined.

' Percent By Boundary of Electrolytes Weight of Tworphase Electrolyte Region, 0.

None. 39 NaClO; (Solubilizer) 2. 42 NaI (Solubilizer) 3.0 47

K4Pz07 (Builder) 6.6 20

This. shows the greater temperature stability achieved with the solubilized phosphine oxide detergents of this invention.

When any of the following compounds, or mixtures thereof, are, substituted, either wholly or in part for the specifically named detergent in the above example, substantially equivalent results are obtained in that more detergents and builders are solubilized with the solubilizing electrolytes than without:

dimethyltetradecylphosphine oxide; diethyldecylphosphine oxide; bis-(Z-hydroxyethyl)hexadecylphosphine oxide; dihydroxymethylpentadecyl phosphine oxide; dipropylundecylphosphine oxide; bis-(Z-hydroxypropyl)tetrapropylene phosphine oxide; bis-(3-hydroxypropyl)oleylphosphine oxide;

the corresponding compounds in which methyl, ethyl, 2- hydroxyethyl, hydroxy methyl, propyl, 2-hydroxypropyl and 3-hydroxy propyl groups are substituted for one of the short chain groups in the above compounds; the corresponding compounds in which decyl, undecyl, dodecyl, tetradecyl, pentadecyl, tridecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, tetrapropylene, diheptene, oleyl, linoleyl, and linolenyl groups are substituted for the long chain group in each of the above compounds.

V 10 Example IV When in the previous examples any of the following solubilizer compounds, or mixtures thereof, are substituted, either wholly or in part, for the specifically named solubilizing electrolytes, substantially equivalent results are obtaiped in that more of the detergents and builders can be formed into homogeneous solutions with the solubilizing electrolytes than without: chlorides, bromides,

iodides, chlorates, nitrites, bromates, iodates, perchlorates,

thiocyanates, periodates, bicarbonates, borates, and niammonium salts.

Example V When in the previous examples any of the following polyvalent electrolytes, or mixtures thereof are substituted, either wholly or in part, for the" specifically named poly valent electrolytes, substantially equivalent results are obtained in that more of the detergents and builders can be formed into homogeneous solutions with the solubilizing electrolytes than without: tripolyphosphates; sulfates; carbonates; pyrophosphates; phosphates; hexametaphosphates; ethylenediamine tetraacetates; N-(Z-hydroxyethyl)-ethylenediaminetriacetates; nitrilotriacetates; N-(2- hydroxyethyl)-nitrilodiacetates; phytates; ethane-l-hydroxy-l,l-diphosphonates; methylene diphosphonates; and ethylidene, isopropylidene, benzylmethylidene and chloromethylidene diphosphonates; salts of polymers of itaconic acid, aconitic acid, maleic acid, mesaconie acid, fumaric acid, methylene malonic acid and citraconic acid and copolymers with themselves and/ or ethylene and/ or acrylic acid in e.g. 1:1 molar ratios and having molecular weights of 75,000; 100,000; and 125,000 (the copolymers with ethylene and/or acrylic acid having equivalent weights, based on the acid form of 65, 70 and 75); in the form of their sodium, potassium, triethanolammonium, diethanolammonium, and monoethanolammonium salts.

What is claimed is:

1. An aqueous homogeneous liquid detergent composition consisting essentially of:

(I) from about 1% to about 40% by weight of the composition of a detergent selected from the group consisting of (A) a detergent having the formula wherein R and R are each selected from the group consisting of hydrogen, methyl, and ethyl groups, R is a straight chain alkylene group containing two to four carbon atoms, and having from 0 to 1 hydroxyl group substituted on a secondary carbon atoms, and R is an alkyl chain of from about 10 to about 20 carbon atoms;

(B) a detergent having the formula R' R R P- O wherein R is selected from the group consisting of alkyl and monohydroxy alkyl radicals containing from about 8 to about 16 carbon atoms and R and R are each selected from the group consisting of alkyl radicals and alkanol radicals containing from one to about three carbon atoms; and (C) mixtures thereof;

(II) from 0% to about 40% by weight of the composition of a polyvalent electrolyte salt selected from the group consisting of (1) sulfates; (2) carbonates; (3) tripolyphosphates; (4) pyrophosphates; (5) orthophosphates; (6) hexametaphosphates; (7) ethylenediaminetetraacetates; (8) N (Z-hydroxyethyl)-ethylenediaminetriacetates; (9) nitrilotriacetates; (10) N- (Z-hydroxyethyl)-nitrilodiacetates; (11) phytates; (12) ethane-1-hydroxy-1,1-diphosphonates; (l3) methylene diphosphonates; (14) eth- 1 1 ylidene diphosphonates; isopropylidene diphosphonates; (16) benzylrnethylidene diphosphonates; (17) chloromethylidene diphosphonates; (18) a polyelectrolyte builder material consisting of watersoluble salts of a polymeric aliphatic polycarboxylic acid selected from the group consisting of (a) water-soluble salt of a homopolymer of an aliphatic polymer of an aliphatic polycarboxylic acid having the following empirical formula:

wherein X, Y, and Z are each selected from the group consisting of hydrogen,

methyl,

carboxyl, and

carboxymethyl, at least one of X, Y, and Z being selected from the group consisting of carboxyl and carboXymethyl, provided that X and Y can be carboxymethyl, only when Z is selected from carboxyl and carboxymethyl, wherein only one of X, Y, and Z can be methyl, and wherein n is a whole integer having a value within a range, the lower limit of which is three and the upper limit of which is determined by the solubility characteristics in an aqueous system;

(b) a water-soluble salt of a copolymer of at least two of the monomeric species having the empirical formula described in (a); and

(c) a water-soluble salt of a copolymer of a member selected from the group of alkylenes and monocarboxylic acids with the aliphatic polycarboxylic compounds described in (a), said copolymers having the general formula:

ti t i H R n Y C O OH in I:

wherein R is selected from the group consisting of hydrogen,

methyl,

carboxyl,

carboxymethyl, and

carboxyethyl; wherein only one R can be methyl; wherein m is at least 45 mole percent of the copolymer; wherein X, Y, and Z are each selected from the group consisting of hydrogen,

methyl,

carboxyl, and

carboxymethyl, at least one of X, Y and Z being selected from the group of carboxyl and carboxymethyl provided that X and Y can be carboxymethyl only when Z is selected from carboxyl and carboXymethyl, wherein only one of X, Y, and Z can be methyl, and wherein n is a whole integer within a range, the lower limit of which is three and the upper limit of which is determined primarily by the solubility characteristics in an aqueous system; said polyelectrolyte builder material having a minimum molecular weight of 350 calculated as the acid form and an equivalent weight of about 50 to about 80, calculated as the acid form; and (19) mixtures thereof, the cations of the above polyvalent electrolytes being selected from the group consisting of sodium, potassium, ammonium, triethanol ammonium, diethanol ammonium and monoethanol ammonium cations and mixtures thereof;

(III) from about 0.5% to about 20% by weight of the composition, and sufiicient to keep the composition homogeneous, of inorganic solubilizing electrolytes selected from the group consisting of sodium, potassium, ammonium, monoethanolammonium, diethanolammonium and triethanolammonium chlorides, bromides, iodides, nitrites, bromates, iodates, chlorates, thiocyanates, perchlorates, nitrates and mixtures thereof; and

(IV) the balance substantially water.

2. The composition of claim 1 wherein the detergent comprises a surface active agent having the formula R R R P O wherein R is selected from the group consisting of alkyl and alkyl monohydroxy radicals containing from about 8 to about 16 carbon atoms and R and R are each selected from the group consisting of alkyl radicals and alkanol radicals containing from one to about three carbon atoms.

3. The liquid detergent composition of claim 1 wherein the R of the detergent is an alkylene chain of three carbon atoms with a hydroxyl group substituted on the middle carbon atom, R and R are methyl groups, and R is a mixture of alkyl groups derived from tallow; and the solubilizing agent is NaCl.

4. A homogeneous liquid detergent composition consisting essentially of:

(1) from about 1% to about 40% by weight of the composition of a detergent having the formula wherein R and R are selected from the group consisting of hydrogen, methyl and ethyl groups, R is an alkylene group containing from two to four carbon atoms, and having from 0 to 1 hydroxyl group substituted on a secondary carbon atom, and R is an alkyl chain of (A) from about 12 to about 18 carbon atoms when R and R are hydrogens, (B) from about 16 to about 20 carbon atoms when R and R are alkyl chains and R is an alkylene chain, and (C) from about 14 to about .18 carbon atoms when R and R are alkyl chains and R is a threecarbon atom alkylene chain with a hydroxyl group substituted on the middle carbon atom;

(2) from about 0.5% to about 20% by weight of the composition of an inorganic electrolyte solubilizing agent selected from the group consisting of sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, and triethanolammonium chlorides, bromides, iodides, nitrites, bromates, iodates, chlorates, thiocyanates, perchlorates, nitrates and mixtures thereof; and

(3) balance water.

5. Thecomposition of claim 1 wherein the detergent has the formula and wherein R and R are each selected from the group consisting of hydrogen, methyl and ethyl groups, R is selected from the group consisting of an unsubstituted alkylene group containing from two to four carbon atoms and an alkylene group of three carbon atoms with a hydroxyl group substituted on the middle carbon atom, and R is an alkyl chain of (A) from about 12 to about 18 carbon atoms when R and R are hydrogens, (B) from about 16 to about 20 carbon atoms when R and R are each selected from the group consisting of methyl and ethyl groups and R is an unsubstituted alkylene group containing from 2 to 4 carbon atoms as hereinbefore described, and (C) from about 14 to about 18 carbon atoms when R and R are selected from the group consisting of methyl and ethyl groups and R is a three carbon 2,950,255 8/1960 Goff 2521'82 atom alkylene group with a hydroxyl group substituted on 3,001,945 9/ 1961 Drew et a1. 252152 the middle carbon atom, as hereinbefore described. 3,086,943 4/1963 Lang 252152 6. The composition of claim 1 wherein the inorganic 3,159,581 12/ 1964 Diehl 252I152 solubilizing electrolyte is selected from the group consist- 5 3,168,478 2/ 1965 Stefcik 252-135 ing of sodium, potassium, ammonium, mouoethanolammonium, diethanolammonium and triethanolammo- OTHER REFERENCES nium nitrites, bromates, iodates, chlorates, thiocyanates, h Mil-31101 Amphoteric Surfa Active Agents perchlorates and nitrates and mixtures thereof. Mi h i Co d 5 Group 150 il 1953 2- t 12 1 References Cited 10 pp 4 5 and 19 UNITED STATES PATENTS LEON D. ROSDOL, Primary Examiner.

2,129,264 9/-1938 Downing et a1. 252152 S. E. DARDEN, Assistant Examiner. 2,768,143 10/1956 Henry 252363.5 

1. AN AQUEOUS HOMOGENEOUS LIQUID DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF: (I) FROM ABOUT 1% TO ABOUT 40% BY WEIGHT OF THE COMPOSITION OF A DETERGENT SELECTED FROM THE GROUP CONSISTING OF (A) A DETERGENT HAVING THE FORMULA 